DUTCH NATIONAL CHEMISTRY OLYMPIAD

PROBLEMS SELECTION ROUND 2

(the week of)
Wednesday 8 April 2009

Specialising in Chemical Translations

This selection round consists of 30 multiple choice questions divided over 8 subjects and
4 open questions consisting of a total of 23 sub questions, as well as an answer sheet for
the multiple choice questions
Use a different answer sheet, with your name on it, for each problem (open questions)
The maximum score for this test is 111 points
This selection round will take 3 hours (180 minutes) maximum.
Resources needed: calculator and BINAS 5th edition
For each problem, the number of points obtained for correct answers, is indicated
 Problem 1 Multiple choice questions (45 points total)

1½ points per correct answer (For each question, write your answer (letter) on the answer
sheet).
Please note: wrong answer –¼ point; no answer: 0 points.

Phase changes:
1 A mixture of pentane and hexane is separated with the
setup shown, by means of fractional distillation.
What temperature will the thermometer read when the
first drop of condensation is forming on it?
boiling point ºC
pentane 36
hexane 69

A less than 36 ºC
B 36 ºC
C between 36 ºC and 69 ºC
D more than 69 ºC

Vertical axis: ln(vapour pressure)

In the diagram, the natural logarithm is shown of the vapour pressure of two substances vs.
. Which conclusions would you draw with regard to the ΔHvapour of substance I compared
to substance II?
Hint: Use the equation in Binas table 37C and the fact that the liquid and gas phases are at
equilibrium at the boiling point.
A ΔHvapour of I is larger than ΔHvapour of II
B ΔHvapour of I is smaller than ΔHvapour of II
C ΔHvapour of I equals ΔHvapour of II
D No conclusion can be drawn from this information only.

3 The freezing point depression of a solution is proportional to the number of dissolved

particles. Which solution will give the smallest freezing point depression?
A 0.1 M solution of
A AlCl3
B CaCl2
C CH3COOH
D HCl

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 2
 Acid-base
4 A standardised solution (i.e. the molarity is accurately known) of potassium hydrogen
phthalate can be used to determine the molarity of a NaOH-solution (caustic soda) by means
of titration. Which approach will give a molarity for the caustic soda which is too low?
A Weighing in half of the recommended amount of potassium hydrogen phthalate.
B Dissolving potassium hydrogen phthalate in more water than prescribed.
C Forgetting to rinse the tap of the burette with caustic soda before titration.
D Loss of a small amount of potassium hydrogen phthalate solution out of the Erlenmeyer
flask before starting the titration.

5 For which equilibrium does the equilibrium constant equal Kz of NH4+?

A NH3(aq) + H2O(l) ⇄ NH4+(aq) + OH (aq)
B NH3(aq) + H3O+(aq) ⇄ NH4+(aq) + H2O(l)
C NH4+(aq) + OH (aq) ⇄ NH3(aq) + H2O(l)
D NH4+(aq) + H2O (l) ⇄ NH3(aq) + H3O+(aq)

6 The diagram shows the titration of a weak monovalent acid. What is/are the pH range(s) of
this acid with its salt?

ml added caustic soda

I pH 4-6 II pH 7-9 III pH 12-13

A I only
B II only
C I and III only
D all ranges

Calculations
7 A number of melted chloride salts are electrolysed with an electric current of 3.00 A. Which
amount of deposited metal would require the longest electrolysis time?
A 50 g Mg
B 75 g Al
C 100 g Ca
D 125 g Fe

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 3
 8 Magnetite, Fe3O4, can be reduced to iron by heating with carbon monoxide according to:
Fe3O4 + 4 CO → 3 Fe + 4 CO2
How much Fe3O4 (in kg) is needed to generate 5.0 kg iron with a yield of 88%?
A 6.1
B 6.9
C 7.9
D 18

9 What is the pH of the solution which is obtained when 45 mL 0.18 M KOH and 65 mL 0.15
M HCl are mixed together?
A 1.07
B 1.13
C 1.82
D 2.92

Physical chemistry: thermodynamics

10 Which standard formation enthalpy of ethyn, C2H2 (in kJ) follows from the information
given below?
reaction equation ΔHº kJ
C2H2 (g) + 2½ O2(g) → 2 CO2(g) + H2O(l) -1299.5
C(s) + O2(g) → CO2(g) -393.5
H2(g) + ½ O2(g) → H2O(l) -285.8

A -1978.8
B -1121.4
C -453.4
D -226.7
E 226.7
F 453.4
G 1121.4
H 1978.8

11 Which statement is always true for a spontaneous reaction?

A The enthalpy change of the system is negative.
B The entropy change of the system is negative.
C The total entropy change is positive.
D The change in free energy of the system is positive.

12 Which value is NOT needed for the calculation of the lattice energy of NaCl by means of a
Born-Haber cycle?
A bond energy of Cl2(g)
B 1st ionisation energy of Cl(g)
C formation enthalpy of NaCl(s)
D sublimation enthalpy of Na(s)

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 4
 13 Which value for the formation enthalpy in kJ mole 1 of Br2(g) follows from the data below?
Sº

Br2(g) 245
Br2(l) 152
A 7
B 12
C 31
D 93

14 Which conclusions can be drawn with regard to the values of ΔGº and Keq of a galvanic
cell?
A ΔGº < 0, Keq < 1
B ΔGº < 0, Keq >1
C ΔGº > 0, Keq < 1
D ΔGº > 0, Keq > 1

Physical chemistry: kinetics

15 Under certain circumstances, the velocity equation of the reaction between CO and NO2, in
which CO2 and NO are formed, is:
s = k[CO][NO2]
What is the unit of reaction constant k?
A

16 The initial velocities of reaction X + Y → Z are given in the table.

[X] (mole L 1) [Y] (mole L 1) s (mole L 1 s 1)

0.10 0.10 0.020
0.10 0.20 0.080
0.30 0.30 0.54
The velocity equation is: s =
A k[X] 2
B k[Y] 2
C k[X][Y]
D k[X][Y] 2

17 The velocity equation for reaction A → B is s = k[A].

After 50.0 minutes, 40.0% of A has been converted.
From this, what can be concluded with regard to reaction constant k in min 1?
A 8.00∙10-3
B 1.02∙10-2
C 1.39∙10-2
D 1.83∙10-2

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 5
 Equilibrium
18 At a certain temperature, 2.00 mole H2(g) and 2.00 mole I2(g) are introduced into a vessel
of 1.00 L. The following equilibrium is established: H2 + I2 ⇄ 2HI. When the equilibrium
has established, 3.50 mole HI is present.
What is the value of the equilibrium constant Kc ?
A 3.7
B 14
C 49
D 2.0∙102

19

Which of the changes below cause(s) of the amount of propene at equilibrium to increase?
I Increase of temperature
II Increase of pressure
A only I
B only II
C both I and II
D neither

20 A saturated solution of Fe(OH)2 has pH = 8.67.

What is the value of the solubility product Ks of Fe(OH)2?
A 5.1∙10-17
B 1.0∙10-16
C 2.3∙10-11
D 4.8∙10-6

Electrons
21 Which series of quantum numbers matches an electron in a 4d-orbit?
n l ml ms
A 4 1 -1 ½
B 4 2 -2 -½
C 4 3 3 ½
D 4 3 -1 -½

22 How many unpaired electrons does a Co+(g)-ion have in its ground state?
A 1
B 3
C 5
D 7

23 Which particle is diamagnetic?

A NO
B N2+
C O2
D O22

24 How many π-bonds does trans-butenedioic acid (C4H4O4) contain?

A 1
B 2
C 3
D 4

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 6
 Structure and properties
25 Which of these molecules have a dipole moment unequal to 0?
I H2C=CHCl II cis-ClHC=CHCl III trans-ClHC=CHCl
A only I
B only III
C only I and II
D I, II and III

26 What is the bond angle of I I I in I3 ? Hint: the negative charge is located on the centre I
and mesomerism does not occur within the particle.
A 90º
B between 90 and 120º
C 120º
D 180º

27 Which particle has the shortest N-O bond?

A NO+
B NO2+
C NO2
D NO3

28 In the gas phase, PCl5 consists of individual molecules, but in the solid phase it has an ionic
structure PCl4+PCl6 .
What are the 3 dimensional structures of these particles?

A
B
C
D

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 7
 29 How many compounds have formula C2H3Cl3?
A 2
B 3
C 4
D 5

30 Cellulose and starch are biopolymers. People can digest starch, but not cellulose. This
difference is mainly due to a difference in
A number of monomer units in both polymers
B identity of the monomers in both polymers
C bond orientation between the monomers
D percentage of carbon in both polymers

Dutch National Chemistry Olympiad 2009 Selection Round 2 Multiple Choice Questions 8
 Open questions (66 points total)
Problem 2 NMR SPECTROSCOPY (24 points)

(NOTE There are 2 NMR spectra with this problem. Below the 1H spectrum, the integrals (=
areas) of the signals are given as numbers ratios).
From the IR spectrum of an unknown substance X with M = 102, we know X to be an ester.

6p 1. Calculate the molecular formula of substance X.

Give all possible structural formulas of substance X.

The correct structural formula can be derived by NMR.

At the end of this problem, you’ll find 2 NMR spectra:
1
H-NMR spectrum I of a solution of X in the solvent CDCl3, to which some TMS has
been added, recorded at a frequency of 300 MHz.
13
C-NMR spectrum II, recorded in the same solution, at a frequency of 75 MHz. The
three small signals in spectrum II around 77 ppm are originating from the solvent.

2p 2. Using the 13C-NMR spectrum, explain how many different C-atoms (i.e. C-atoms with
different surroundings) can be found in a molecule of substance X.

3p 3. Calculate the total integral.

You know from question 1 to how many H-atoms this corresponds.
Next, using the integral, calculate the number of H-atoms per -value,.

1p 4. Why doesn’t B show a split signal?

3p 5. For H’s of the signal at 1.65 ppm, explain with how many neighbouring H’s they are coupled.
At which -value(s) can these neighbouring H’s be found?

2p 6. Explain why the H’s resonating in signal A are the only ones with such a high -value.

3p 7. Explain the structure of R1 in substance X (the ester RCOOR1).

Explain the structure of the R-group.
Give the structural formula of substance X.

4p 8. In the structural formula of substance X, put the correct signal position in ppm with each C-
atom (13C-NMR spectrum).

Dutch National Chemistry Olympiad 2009 Selection Round 2 Open Questions 9

 1
H NMR spectrum I of substance X in CDCl3 at 300 MHz

13
C NMR spectrum II of substance X in CDCl3 at 75 MHz

Dutch National Chemistry Olympiad 2009 Selection Round 2 Open Questions 10

 Problem 3 Williamson reaction (15 points)

One application for solutions of sodium alkanolates in an alkanol solution is the so called
Williamson reaction. A reaction in which an alkoxyalkane is obtained when a solution of an
alkanolate reacts with a halogenalkane, is called a Williamson reaction. A solution of sodium
methanolate in methanol contains, apart from CH3OH molecules, also Na+ ions and CH3O
ions. With the Williamson reaction occurring when this solution reacts with chloroethane,
CH3O ions will react with CH3CH2Cl molecules, forming methoxyethane:

CH3O + Cl CH2 CH3 → CH3 O CH2 CH3 + Cl

Methoxyethane can also be formed in a different way other than via a Williamson reaction.
Different particles, other than CH3O and CH3CH2Cl, will have to react with each other.

2p 9. Give the formulas of these other particles.

When a solution of sodium methanolate in methanol reacts with chloroethane, another

reaction will take place apart from the Williamson reaction. With this other reaction, ethene is
formed:

CH3O + Cl CH2 CH3 → CH3OH + CH2= CH2 + Cl

Alkene formation can occur if a solution of sodium methanolate in methanol reacts with a
chloroalkane containing at least 2 C-atoms per molecule.
One could imagine the formation of an alkene from CH3O and such a chloroalkane to
proceed according to the following two partial reactions:

Partial reaction 1: a CH3O -ion extracts a H+-ion from the chloroalkane. Only H-atoms bonded
to a C-atom next to the C-atom to which the Cl-atom is bonded, are suitable for donation of
the H+-ion.

Partial reaction 2: a Cl -ion separates from the ion formed in partial reaction 1, forming an
alkene molecule.

2p 10. Give the electron formula of the ion formed in partial reaction 1, when a H+-ion is extracted
from the chloroethane. In the electron formula, put the charge with the correct atom.

For some monochloroalkanes, with at least 2 C-atoms per molecule, no alkene formation will
take place during a reaction with a solution of sodium methanolate in methanol.

2p 11. Give the structural formula of such a monochloroalkane.

Also during a reaction of 2-chloropentane, CH3-CHCl-CH2-CH2-CH3, with a solution of

sodium methanolate in methanol, both the Williamson reaction and alkene formation take
place. It has been shown that three alkenes are formed in this process.

Dutch National Chemistry Olympiad 2009 Selection Round 2 Open Questions 11

1p 12. Give the names of these three alkenes.

The Williamson reaction, occurring when a solution of sodium methanolate in methanol reacts
with 2-chloropentane, kan be described by an equation in the following way:

CH3O + CH3-CHCl-CH2-CH2-CH3 → CH3-CH(OCH3)-CH2- CH2-CH3 + Cl

There are 2 optical isomers of 2-chloropentane: a R-isomer and a S-isomer. There are also 2
optical isomers of 2-methoxypentane. If only (optical active) R-2-chloropentane reacts with a
solution of sodium methanolate in methanol, both optical isomers of 2-methoxypentane are
formed. As it turns out, a reaction mixture is obtained in which R-2 methoxypentane and S-2-
methoxypentane are present in molar ratio 2: 3.

3p 13. Explain whether this mixture will show optical activity.

It is possible to prepare R-2-methoxypentane without formation of S-2-methoxypentane. This

can be done via a Williamson reaction, but one would have to use a chloroalkane other than
(R-)2-chloropentane and a solution of an alkanolate other than methanolate.

2p 14. Give the names of the alkanolate and the chloroalkane needed for the Williamson reaction
which gives R-2-methoxypentane without the formation of S-2-methoxypentane.

2p 15. Explain why no S-2-methoxypentane is formed during the Williamson reaction between these
two types of particles.

Problem 4 Industrial production of hydrogen (14 points)

In industry, hydrogen can be produced by heating hydrocarbons, like methane, with steam:

CH4(g) + H2O(g) → 3 H2(g) + CO(g)

3p 16. Calculate the Gibbs change of energy ΔrGº of this reaction and, in doing so, the equilibrium
constant Kp. Also indicate the unit of Kp.

2p 17. How does the value of equilibrium constant Kp change with temperature?

The industrial production can take place without a catalyst at atmospheric pressure and high
temperature. At equilibrium, usually 0.20 volume% methane gas remains.

7p 18. Calculate the value of Kp for this industrial process which gives 0.20 volume% methane gas at
equilibrium. Assume that the reactions starts with equal amounts of methane and steam.
Note: the conditions are far from standard.

2p 19. Estimate, using the Van ‘t Hoff-relation the temperature needed to

produce hydrogen from methane in industry.

Dutch National Chemistry Olympiad 2009 Selection Round 2 Open Questions 12

 Problem 5 Interstellar chemistry (13 points)

A possible ion-molecule reaction mechanism for the synthesis of ammonia in interstellar gas
clouds is given below:

N+ + H2 → NH+ + H k1
NH+ + H2 → NH2+ + H k2
NH2+ + H2 → NH3+ + H k3
NH3+ + H2 → NH4+ + H k4
NH4+ + e → NH3 + H k5
NH4+ + e → NH2 + 2 H k6

5p 20. Show the relations between the concentrations of the intermediates NH+, NH2+, NH3+ and
NH4+ and the concentrations of the reactants: [N+], [H2] and [e ]. Use the steady state
approximation.

3p 21. Show that the overall production rate of NH3 is given by: .
nd
In this equation, k2 is the 2 order reaction constant of the reaction. Express k2e in the reaction
rate constants of the partial steps k1, k5 and k6.

2p 22. What is the cause of the activation energy in a chemical reaction?

The reaction rates of many ion-molecule reactions are almost independent of temperature.

3p 23. What can be concluded from this with regard to the activation energy?
Explain why this conclusion is important for reactions taking place in interstellar space.

Dutch National Chemistry Olympiad 2009 Selection Round 2 Open Questions 13